U.S. patent number 10,662,069 [Application Number 16/015,115] was granted by the patent office on 2020-05-26 for crystalline metallophosphates, their method of preparation, and use.
The grantee listed for this patent is UOP LLC. Invention is credited to Mark A. Miller, John P. S. Mowat, Mimoza Sylejmani-Rekaliu, Kristine N. Wilson, Benjamin D. Yuhas.
United States Patent |
10,662,069 |
Yuhas , et al. |
May 26, 2020 |
Crystalline metallophosphates, their method of preparation, and
use
Abstract
A new family of crystalline microporous metallophosphates
designated AlPO-90 has been synthesized. These metallophosphates
are represented by the empirical formula
R.sup.+.sub.rM.sub.m.sup.2+EP.sub.xSi.sub.yO.sub.z where R is an
organoammonium cation, M is a framework metal alkaline earth or
transition metal of valence +2, and E is a trivalent framework
element such as aluminum or gallium. The AlPO-90 compositions are
characterized by a new unique ABC-6 net structure, and have
catalytic properties suitable for carrying out various hydrocarbon
conversion processes, as well as characteristics suitable for the
efficient adsorption of water vapor in a variety of applications,
such as adsorption heat pumps.
Inventors: |
Yuhas; Benjamin D. (Evanston,
IL), Wilson; Kristine N. (Elgin, IL), Miller; Mark A.
(Niles, IL), Sylejmani-Rekaliu; Mimoza (Bensenville, IL),
Mowat; John P. S. (Arlington Heights, IL) |
Applicant: |
Name |
City |
State |
Country |
Type |
UOP LLC |
Des Plaines |
IL |
US |
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Family
ID: |
68980555 |
Appl.
No.: |
16/015,115 |
Filed: |
June 21, 2018 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20190389733 A1 |
Dec 26, 2019 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
B01J
20/3085 (20130101); B01J 23/8913 (20130101); B01J
37/0018 (20130101); B01J 37/031 (20130101); B01J
29/85 (20130101); C01B 39/54 (20130101); B01J
37/036 (20130101); B01D 53/261 (20130101); B01J
37/10 (20130101); B01J 23/74 (20130101); B01J
35/002 (20130101); B01D 53/04 (20130101); B01J
20/18 (20130101); B01D 53/02 (20130101); B01J
29/83 (20130101); B01J 37/04 (20130101); B01J
20/3057 (20130101); Y02P 30/42 (20151101); B01D
2253/116 (20130101); Y02P 20/129 (20151101); B01D
2257/80 (20130101) |
Current International
Class: |
C01B
39/54 (20060101); B01J 29/85 (20060101); B01J
37/04 (20060101); B01J 37/10 (20060101); B01D
53/26 (20060101); B01J 20/30 (20060101); B01J
20/18 (20060101); B01D 53/04 (20060101); B01J
37/00 (20060101) |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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2867166 |
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Mar 2017 |
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EP |
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WO-2017205091 |
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May 2017 |
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WO |
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Other References
Smith et al., Enumeration of 4-connected 3-dimensional nets and
classification of framework silicates: the infinite set of ABC-6
nets; the Archimedian and .sigma.-related nets; American
Mineralogist, vol. 66, pp. 777-788, 1981. cited by applicant .
Xie et al., "SSZ-52, a Zeolite with an 18-Layer Aluminosilicate
Framework Structure RElated to That of the DeNOx Catalyst
Cu-SSZ-13", Journal of the American Chemical Society, 2013, 135,
10519-10524, 2013. cited by applicant .
Van Heyden, Kinetics of Water Adsorption in Microporous
Aluminophosphate layers for regenerative heat exchangers, Applied
Thermal Engineering, 29 (2009) 1514-1522. cited by applicant .
Wright et al., Cation-directed syntheses of novel zeolite-like
metalloaluminophosphates STA-6 and STA-7 in the presence of
azamacrocycle templates, J. Chem. Sc=oc., Dalton Trans., 2000, pp.
1243-1248. cited by applicant .
Schreyeck et al., The diaza-polyoxa-macrocycle `Kryptofix222` as a
new template for the synth esis of LTA-type-AIPO4 Co-templating
role of F and/or (CH3)4N+ ions, Micorporous and Mesoporous
Materials 22 (1998) 87-106. cited by applicant .
De Lange et al., Adsorption-Driven Heat Pumps: The Potential of
Metal-Organic Frameworks, Chem. Rev. 2015, 115, 12205-12250,
American Chemical Society. cited by applicant .
Meier et al., Zeolite Structure Type EAB: Crystal Structure and
Mechanism for the Topotactic Transformation of the Na, TMA Form,
Journal of Solid State Chemistry, 37, 204-218 (1981), Academic
Press. cited by applicant .
Turrina et al., STA-20: An ABC-6 Zeotype Structure Prepared by
Co-Templating and Solved via a Hypothetical Structure Database and
STEM-ADF Imaging, Chemistry of Materials, ACS Publications, 2017.
cited by applicant .
Li et al.,Nature Communications, DOI: 10.1038/ncomms9328, 2015,
Macmillan Publishers Limited. cited by applicant.
|
Primary Examiner: Brooks; Clinton A
Claims
The invention claimed is:
1. A microporous crystalline material that has an empirical
composition in an as-synthesized form and on an anhydrous basis
expressed by an empirical formula:
C.sub.c.sup.+A.sub.a.sup.+M.sub.m.sup.2+EP.sub.xSi.sub.yO.sub.z
where M is at least one framework divalent cation and is selected
from the group consisting of alkaline earth and transition metals,
wherein M is a cation selected from the group consisting of
beryllium, magnesium, cobalt (II), manganese, zinc, iron(II),
nickel and mixtures thereof, C is a cyclic organoammonium cation, A
is an acyclic organoammonium cation, the ratio (c/a) having a value
from 0.01 to about 100, and the sum (c+a) representing the mole
ratio of (C+A) to E and has a value of about 0.1 to about 2.0, "m"
is the mole ratio of M to E and varies from 0 to about 1.0, "x" is
a mole ratio of P to E and varies from 0.5 to about 2.0, a ratio of
silicon to E is represented by "y" which varies from about 0 to
about 1.0, E is a trivalent element which is tetrahedrally
coordinated, is present in the framework, and is selected from the
group consisting of aluminum, gallium, iron(III) and boron and "z"
is a mole ratio of O to E and is given by an equation:
z=(2m+c+a+3+5x+4y)/2 and is characterized by a following x-ray
diffraction pattern, having at least the d-spacings and relative
intensities set forth in Table 1: TABLE-US-00018 TABLE 1 2-theta
(.degree.) d (.ANG.) Intensity 9.86-9.91 8.96-8.91 w-m 13.97-14.10
6.34-6.28 m 17.21-17.26 5.15-5.13 vw-w 18.79-18.91 4.72-4.68 vw-w
19.78-19.87 4.49-4.46 m-s 22.19-22.33 4.01-3.97 w-m 23.57-23.63
3.78-3.76 w 24.36-24.50 3.66-3.63 vs 27.55-27.61 3.24-3.22 w-m
28.16-28.37 3.17-3.14 m 31.51-31.69 2.84-2.82 w-m 33.26-33.37
2.70-2.68 vw 34.32-34.86 2.62-2.57 w-m 42.59-42.91 2.13-2.10 vw-w
47.70-47.90 1.91-1.89 vw-w 51.92-52.37 1.76-1.74 w-m.
2. The microporous crystalline material of claim 1 wherein after
being calcined said AlPO-90 material is characterized by the x-ray
diffraction pattern, having at least the d-spacings and relative
intensities set forth in Table 2 below: TABLE-US-00019 TABLE 2
2-theta (.degree.) d (.ANG.) Intensity 9.96-10.05 8.87-8.79 w
14.13-14.17 6.27-6.24 vs 19.23-19.32 4.62-4.59 vw-m 20.06-20.10
4.43-4.41 w-m 22.41-22.49 3.97-3.95 vw-m 24.02-24.65 3.71-3.60 m-vs
27.88-27.98 3.20-3.18 w-m 28.38-28.54 3.15-3.12 m 31.89-31.98
2.81-2.79 w 35.05-35.12 2.56-2.55 w 52.60-52.81 1.74-1.73 vw.
3. The microporous crystalline material of claim 1 characterized on
an anhydrous basis by the empirical formula:
H.sub.wM.sub.m.sup.2+EP.sub.xSi.sub.yO.sub.z where M is at least
one metal cation of valence+2 selected from the group consisting of
Be.sup.2+, Mg.sup.2+, Zn.sup.2+, Co.sup.2+, Mn.sup.2+, Fe.sup.2+,
Ni.sup.2+, "m" is the mole ratio of M to E and varies from 0 to
about 1.0, H is a proton, w'' is the mole ratio of H to E and
varies from 0 to 2.5, E is a trivalent element selected from the
group consisting of aluminum, gallium, iron, boron and mixtures
thereof, "x" is mole ratio of P to E and varies from 0.5 to about
2.0, "y" is the mole ratio of Si to E and varies from 0.05 to about
1.0, "m"+"y".gtoreq.0.1, and "z" is the mole ratio of O to E and
has a value determined by the equation: z=(w+2m+3+5x+4y)/2.
4. The microporous crystalline material of claim 1 that indexes on
a unit cell with hexagonal axes with lattice parameters a=12.768
.ANG. and c=15.333 .ANG. and has an ABC-6 net structure with the
stacking sequence repeating every 6 layers along the c-axis
(p=15.333/2.5=6.13).
5. The microporous crystalline material of claim 4 that can be
described as a combination of two zeotypes with stacking sequences
of AABCBC and ABACBC.
6. The microporous crystalline material of claim 5 where the
percentage of AABCBC zeotype can be defined as x and the percentage
of ABACBC zeotype can be defined as (100-x), where x ranges from
0-100, inclusive.
Description
BACKGROUND OF THE INVENTION
This invention relates to a novel family of metallophosphates,
collectively designated AlPO-90. They are represented by the
empirical formula:
C.sub.c.sup.+A.sub.a.sup.+M.sub.m.sup.2+EP.sub.xSi.sub.yO.sub.z
where M is a divalent framework metal such as magnesium or zinc, C
is a cyclic organoammonium cation, A is an acyclic organoammonium
cation, and E is a trivalent framework element such as aluminum or
gallium.
Classes of molecular sieves include crystalline aluminophosphate,
silicoaluminophosphate, or metalloaluminophosphate compositions
which are microporous and which are formed from corner sharing
AlO.sub.4/2 and PO.sub.4/2 tetrahedra. In 1982, Wilson et al. first
reported aluminophosphate molecular sieves, the so-called AlPOs,
which are microporous materials that have many of the same
properties as zeolites, although they do not contain silica (See
U.S. Pat. No. 4,310,440). Subsequently, charge was introduced to
the neutral aluminophosphate frameworks via the substitution of
SiO.sub.4/2 tetrahedra for PO.sub.4/2.sup.+ tetrahedra to produce
the SAPO molecular sieves as described by Lok et al. (See U.S. Pat.
No. 4,440,871). Another way to introduce framework charge to
neutral aluminophosphates is to substitute
[Me.sup.2+O.sub.4/2].sup.2- tetrahedra for AlO.sub.4/2.sup.-
tetrahedra, which yields the MeAPO molecular sieves (see U.S. Pat.
No. 4,567,029). It is furthermore possible to introduce framework
charge on AlPO-based molecular sieves via the simultaneous
introduction of SiO.sub.4/2 and [M.sup.2+O.sub.4/2].sup.2-
tetrahedra to the framework, giving MeAPSO molecular sieves (See
U.S. Pat. No. 4,973,785).
Numerous molecular sieves, both naturally occurring and
synthetically prepared, are used in various industrial processes.
Synthetically, these molecular sieves are prepared via hydrothermal
synthesis employing suitable sources of Si, Al, P, metals, and
structure directing agents such as amines or organoammonium
cations. The structure directing agents reside in the pores of the
molecular sieve and are largely responsible for the particular
structure that is ultimately formed. These species may balance the
framework charge associated with silicon or other metals such as Zn
or Mg in the aluminophosphate compositions, and can also serve as
space fillers to stabilize the tetrahedral framework. A particular
synthetic scheme utilizes multiple structure-directing agents in
the same gel in order to direct the formation of multiple cages or
cavities. This has been demonstrated for aluminosilicates, such as
UZM-5 (U.S. Pat. No. 8,747,807), as well as
silicoaluminophosphates, such as STA-20 (Turrina et al., Chem.
Mater., 29, 2180 (2017)).
Molecular sieves are characterized by having pore openings of
uniform dimensions, having a significant ion exchange capacity, and
being capable of reversibly desorbing an adsorbed phase which is
dispersed throughout the internal voids of the crystal without
significantly displacing any atoms which make up the permanent
molecular sieve crystal structure. Molecular sieves can be used for
separation applications, in which certain species of a mixed liquid
or vapor stream are captured within the pores of the molecular
sieve, and others are excluded. Molecular sieves can also be used
as catalysts for hydrocarbon conversion reactions, which can take
place on outside surfaces as well as on internal surfaces within
the pore.
As stated above, molecular sieves are capable of reversibly
adsorbing and desorbing certain molecules depending on the
adsorbate's size and the molecular sieve's internal pore structure.
There are many applications where it is desired to adsorb water
vapor, preferably in a reversible manner. One such application is
an adsorption heat pump, which is a device that can be used to
recover energy from exhaust or waste heat. As such, adsorption heat
pumps can be utilized to maximize energy efficiency in an
environmentally friendly manner. Molecular sieves can be useful
materials to act as water vapor adsorbents in an adsorption heat
pump due to their high capacity for water vapor. A description of
the use of adsorbents in adsorption heat pumps can be found in U.S.
Pat. No. 8,323,747, incorporated by reference herein in its
entirety.
The type of molecular sieves used in adsorption heat pumps must
meet certain requirements for optimal performance. A high overall
capacity for water vapor is important, but most critically, they
should fully desorb all adsorbed water at no greater than
100.degree. C. Otherwise, too much heat must be applied to fully
remove the adsorbed water from the micropores (i.e., the
regeneration temperature is too high), thus requiring too high of
an energy input. The majority of aluminosilicates (i.e., zeolites)
have rapid uptake of water vapor at very low pressures (P/P.sub.0),
which conversely leads to an unacceptably high regeneration
temperature, despite a high overall capacity for water vapor.
Aluminophosphates and silicoaluminophosphates have been shown to
have more favorable adsorption characteristics for water vapor
(see, for example, M. F. de Lange et al. Chem. Rev. 115, 12205
(2015); H. van Heyden et al. Appl. Therm. Eng. 29, 1514 (2009). In
particular, the materials SAPO-34 and SAPO-5 (zeotypes CHA and AFI,
respectively) have been shown to have particular utility as
adsorbent materials in adsorption heat pumps (see U.S. Pat. Nos.
7,422,993, 9,517,942).
SUMMARY OF THE INVENTION
As stated, the present invention relates to a new family of
metallophosphate molecular sieves, collectively designated AlPO-90.
Accordingly, one embodiment of the invention is a microporous
crystalline material having a three-dimensional framework of at
least EO.sub.4/2 and PO.sub.4/2.sup.+ tetrahedral units and
optionally, at least one of [M.sup.2+O.sub.4/2].sup.2- and
SiO.sub.4/2 tetrahedral units and an empirical composition in the
as-synthesized form and anhydrous basis expressed by an empirical
formula of:
C.sub.c.sup.+A.sub.a.sup.+M.sub.m.sup.2+EP.sub.xSi.sub.yO.sub.z
where M is at least one metal cation of valence +2 selected from
the group consisting of Be.sup.2+, Mg.sup.2+, Zn.sup.2+, Co.sup.2+,
Mn.sup.2+, Fe.sup.2+, N.sup.2+, "m" is the mole ratio of M to E and
varies from 0 to about 1.0, C is a cyclic organoammonium cation,
and A is an acyclic organoammonium cation. The ratio c/a can have a
value from 0.01 to about 100, and the sum (c+a) represents the mole
ratio of (C+A) to E and has a value of about 0.1 to about 2.0. E is
a trivalent element selected from the group consisting of aluminum,
gallium, iron, boron and mixtures thereof, "x" is mole ratio of P
to E and varies from 0.5 to about 2.0, "y" is the mole ratio of Si
to E and varies from 0 to about 1.0, and "z" is the mole ratio of 0
to E and has a value determined by the equation:
z=(2m+c+a+3+5x+4y)/2
The invention is characterized in that it has the x-ray diffraction
pattern having at least the d-spacings and intensities set forth in
Table 1:
TABLE-US-00001 TABLE 1 2-theta (.degree.) d (.ANG.) Intensity
9.86-9.91 8.96-8.91 w-m 13.97-14.10 6.34-6.28 m 17.21-17.26
5.15-5.13 vw-w 18.79-18.91 4.72-4.68 vw-w 19.78-19.87 4.49-4.46 m-s
22.19-22.33 4.01-3.97 w-m 23.57-23.63 3.78-3.76 w 24.36-24.50
3.66-3.63 vs 27.55-27.61 3.24-3.22 w-m 28.16-28.37 3.17-3.14 m
31.51-31.69 2.84-2.82 w-m 33.26-33.37 2.70-2.68 vw 34.32-34.86
2.62-2.57 w-m 42.59-42.91 2.13-2.10 vw-w 47.70-47.90 1.91-1.89 vw-w
51.92-52.37 1.76-1.74 w-m
Another embodiment of the invention is a microporous crystalline
material having a three-dimensional framework of at least
EO.sub.4/2.sup.- and PO.sub.4/2.sup.+ tetrahedral units and
optionally, at least one of [M.sup.2+O.sub.4/2].sup.2- and
SiO.sub.4/2 tetrahedral units and an empirical composition in the
calcined form and anhydrous basis expressed by an empirical formula
of: H.sub.wM.sub.m.sup.2+EP.sub.xSi.sub.yO.sub.z
where "m", "x", "y" are as described above, H is a proton, "w" is
the mole ratio of H to E and varies from 0 to 2.5, and "z" is the
mole ratio of 0 to E and has a value determined by the equation:
z=(w+2m+3+5x+4y)/2 and the invention is characterized in that it
has the x-ray diffraction pattern having at least the d-spacings
and intensities set forth in Table 2:
TABLE-US-00002 TABLE 2 2-theta (.degree.) d (.ANG.) Intensity
9.96-10.05 8.87-8.79 w 14.13-14.17 6.27-6.24 vs 19.23-19.32
4.62-4.59 vw-m 20.06-20.10 4.43-4.41 w-m 22.41-22.49 3.97-3.95 vw-m
24.02-24.65 3.71-3.60 m-vs 27.88-27.98 3.20-3.18 w-m 28.38-28.54
3.15-3.12 m 31.89-31.98 2.81-2.79 w 35.05-35.12 2.56-2.55 w
52.60-52.81 1.74-1.73 vw
Another embodiment of the invention is a process for preparing the
crystalline microporous metallophosphate molecular sieve described
above. The process comprises forming a reaction mixture containing
reactive sources of C, A, E, P, one or both of M and Si, and
heating the reaction mixture at a temperature of about 60.degree.
C. to about 200.degree. C. for a time sufficient to form the
molecular sieve, the reaction mixture having a composition
expressed in terms of mole ratios of the oxides of:
aA.sub.2O:bC.sub.2O:cMO:E.sub.2O.sub.3:dP.sub.2O.sub.5:eSiO.sub.2:fH.sub.-
2O where "a" has a value of about 0.01 to about 5, "b" has a value
of about 0.01 to about 5, "c" has a value of about 0 to about 2,
"d" has a value of about 0.5 to about 8, "e" has a value of about 0
to about 4, and "f" has a value from 30 to 1000.
Yet another embodiment of the invention is a hydrocarbon conversion
process using the above-described molecular sieve as a catalyst.
The process comprises contacting at least one hydrocarbon with the
molecular sieve at conversion conditions to generate at least one
converted hydrocarbon.
Still another embodiment of the invention is an adsorption process
using the crystalline AlPO-90 material. The process may involve the
adsorption and desorption of water vapor over AlPO-90 in an
adsorption heat pump-type apparatus. Separation of molecular
species can be based either on the molecular size (kinetic
diameter) or on the degree of polarity of the molecular species.
Removing contaminants may be by ion exchange with the molecular
sieve.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a scanning electron microscope (SEM) image of an
exemplary AlPO-90 material according to an embodiment described
herein.
FIG. 2 is an x-ray diffraction pattern of an exemplary AlPO-90
material in the as-synthesized form.
FIG. 3 is an x-ray diffraction pattern of an exemplary AlPO-90
material in the calcined form.
DETAILED DESCRIPTION OF THE INVENTION
Applicants have prepared a family of metallophosphate materials
whose topological structure is unique. In their paper "Enumeration
of 4-connected 3-dimensional nets and classification of framework
silicates: the infinite set of ABC-6 nets; the Archimedean and
.sigma.-related nets," Smith and Bennett state "To a first
approximation, all silicates belonging to the ABC-6net family have
x-ray diffraction patterns which can be indexed on a hexagonal
prismatic unit cell with lattice parameters a .about.13.0.+-.0.3
.ANG. and c.about.p.times.(2.6.+-.0.1 .ANG.)." (See American
Mineralogist, 66, 777-788 (1981)). This finding has subsequently
been confirmed by others (see, for example, D. Xie et al. J. Am.
Chem. Soc. 135, 10519 (2013)) as the ABC-6 family has expanded.
One particular composition of AlPO-90 indexes on a unit cell with
hexagonal axes with lattice parameters a=12.559 .ANG. and c=15.333
.ANG., which is suggests an ABC-6 net structure with the stacking
sequence repeating every 6 layers along the c-axis
(p=15.333/2.5=6.13). In the prior art, Meier and Groner enumerated
the 10 possible stacking sequences for a 6-layer molecular sieve
with hexagonal symmetry in 1981 (J. Solid State Chem., 37, 204
(1981)). This finding was later confirmed by Li et al. in 2015
(Nat. Commun. 2015, 6, 8328). At the time of these publications,
only 4 of the 10 possible 6-layer stacking sequences had been
experimentally realized in the prior art (zeotypes CHA, ERI, LIO,
and EAB). Because there are many potential stacking sequences
possible for a given ABC-6 material, the fact that a material has
similar lattice parameters to a known material in the prior art
does not automatically imply that the two materials are identical.
Through a combination of x-ray diffraction experimental techniques
as well as modeling, applicants have determined that AlPO-90 can be
described as a combination of two novel zeotypes, which have
stacking sequences of AABCBC and ABACBC. Although these zeotypes
have been theoretically predicted to exist, the instant material
AlPO-90, with its unique topological connectivity, represents the
first experimental realization of these structures.
The instant microporous crystalline material (AlPO-90) has an
empirical composition in the as-synthesized form and on an
anhydrous basis expressed by the empirical formula:
C.sub.c.sup.+A.sub.a.sup.+M.sub.m.sup.2+EP.sub.xSi.sub.yO.sub.z
where M is at least one framework divalent cation and is selected
from the group consisting of alkaline earth and transition metals.
Specific examples of the M cations include but are not limited to
beryllium, magnesium, cobalt (II), manganese, zinc, iron(II),
nickel and mixtures thereof. C is a cyclic organoammonium cation,
and A is an acyclic organoammonium cation. The ratio c/a can have a
value from 0.01 to about 100, and the sum (c+a) represents the mole
ratio of (C+A) to E and has a value of about 0.1 to about 2.0. The
value of "m" is the mole ratio of M to E and varies from 0 to about
1.0, "x" is mole ratio of P to E and varies from 0.5 to about 2.0.
The ratio of silicon to E is represented by "y" which varies from
about 0 to about 1.0. E is a trivalent element which is
tetrahedrally coordinated, is present in the framework, and is
selected from the group consisting of aluminum, gallium, iron(III)
and boron. Lastly, "z" is the mole ratio of 0 to E and is given by
the equation: z=(2m+r+3+5x+4y)/2.
Synthesis of molecular sieve materials often relies on the use of
organoamino or organoammonium templates known as organic structure
directing agents (OSDAs). While simple OSDAs such as
tetramethylammonium, tetraethylammonium and tetrapropylammonium are
commercially available, oftentimes OSDAs are complicated molecules
that are difficult and expensive to synthesize. However, their
importance lies in their ability to impart aspects of their
structural features to the molecular sieve to yield a desirable
pore structure. For example, the use of
1,4,7,10,13,16-hexamethyl-1,4,7,10,13,16-hexaazacyclooctadecane as
OSDA has been shown to allow synthesis of STA-7, an
aluminophosphate based material of the SAV zeotype (Wright et. al.
J. Chem. Soc., Dalton Trans., 2000, 1243-1248); the use of
4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane
(`Kryptofix 222`) led to the synthesis of AlPO4-42 (Schreyeck et.
al. Micro. Meso. Mater. 1998, 22, 87-106); MAPO-35, a magnesium
aluminophosphate material with the LEV topology, is disclosed in
U.S. Pat. No. 4,567,029 in which quinuclidine is employed as a
structure directing agent; and in U.S. Pat. No. 4,973,785, the
MeAPSO composition CoAPSO-35 is disclosed, which contains both
cobalt and silicon in the framework in addition to Al and P and
uses methylquinuclidine as the structure directing agent.
The art clearly shows that use of complex organoammonium SDAs often
results in new molecular sieve materials. However, the synthesis of
these complicated organoammonium compounds is quite lengthy and
requires many steps, often in an organic solvent, thereby hindering
development of the new molecular sieve material. Frequently, even
for simple, commercially available OSDAs, the OSDA is the most
costly ingredient used in synthesizing molecular sieve materials.
Consequently, it would be economically advantageous to synthesize
new molecular sieves from either commercially available
organoammonium SDAs or SDAs which may be readily synthesized from
commercially available starting materials. This has recently been
demonstrated in an elegant fashion using simple aqueous chemistry
to generate a novel family of organo-1-oxa-4-azonium cyclohexane
compounds (U.S. Pat. No. 9,522,896), derived from morpholino-based
compounds. The procedures described in U.S. Pat. No. 9,522,896 can
be extended to the family of piperidine-based compounds as well.
This procedure thereby allows the preparation of SDAs, such as
unusual quaternary ammonium salts, from readily available starting
reagents in a facile and practical manner. OSDAs prepared by the
methods of the present invention are in aqueous solution and do not
pose odor and flashpoint concerns. The result is the unprecedented
ability to remove the cooling step typically required in the
preparation of in-situ zeolite reaction mixtures and to avoid
purification steps such as evaporation of organic solvent typically
required in ex-situ preparation methods. The obtained
organoammonium bromide salt can be ion-exchanged, either by
reaction with Ag.sub.2O or by anion exchange resins to yield the
hydroxide form of the organoammonium compound, or used as the
halogen salt directly. Finally, the resultant organoammonium
compound can be used for the synthesis of a zeolite or molecular
sieve.
The microporous crystalline metallophosphate AlPO-90 is prepared by
a hydrothermal crystallization of a reaction mixture prepared by
combining reactive sources of C, A, E, phosphorus, and one or both
of M and silicon. A preferred form of the AlPO-90 materials is when
E is Al. The sources of aluminum include but are not limited to
aluminum alkoxides, precipitated aluminas, aluminum metal, aluminum
hydroxide, aluminum salts and alumina sols. Specific examples of
aluminum alkoxides include, but are not limited to aluminum ortho
sec-butoxide and aluminum ortho isopropoxide. Sources of phosphorus
include, but are not limited to, orthophosphoric acid, phosphorus
pentoxide, and ammonium dihydrogen phosphate. Sources of silica
include but are not limited to tetraethylorthosilicate, colloidal
silica, and precipitated silica. Sources of the other E elements
include but are not limited to organoammonium borates, boric acid,
precipitated gallium oxyhydroxide, gallium sulfate, ferric sulfate,
and ferric chloride. Sources of the M metals include the halide
salts, nitrate salts, acetate salts, and sulfate salts of the
respective alkaline earth and transition metals.
One component of C may be an organoammonium cation prepared from
the reaction of an aqueous mixture of a cyclic secondary amine and
an organic dihalide. Specific examples of cyclic secondary amines
include, without limitation, piperidine, homopiperidine,
pyrrolidine, and morpholine. Specific examples of organic dihalides
include, without limitation, 1,4-dibromobutane, 1,5-dibromopentane,
and 1,6-dibromohexane.
In one embodiment, the cyclic secondary amine is piperidine and the
organic dihalide is 1,4-dibromobutane. In another embodiment, the
cyclic secondary amine is piperidine and the organic dihalide is
1,4-dibromopentane. In another embodiment, the cyclic secondary
amine is piperidine and the organic dihalide is 1,5-dibromopentane.
In another embodiment, the cyclic secondary amine is pyrrolidine
and the organic dihalide is 1,4-dibromobutane.
One component of A may be a tetraalkylammonium cation, represented
as NR.sub.4.sup.+. The R groups are chosen such that is the cation
A is acyclic, and there may be multiple distinct R groups on the
same quaternary nitrogen. A particular R group may have the formula
C.sub.nH.sub.2n+1, where n is a whole number ranging from 1 to 4,
inclusive. Non-limiting examples of component A include
tetramethylammonium, ethyltrimethylammonium,
diethyldimethylammonium, methyltriethylammonium,
tetraethylammonium, tetrapropylammonium, propyltrimethylammonium,
butyltrimethylammonium, dipropyldimethylammonium, and
methylethyldipropylammonium.
The reaction mixture containing reactive sources of the desired
components can be described in terms of molar ratios of the oxides
by the formula:
aA.sub.2O:bC.sub.2O:cMO:E.sub.2O.sub.3:dP.sub.2O.sub.5:eSiO.sub.-
2:fH.sub.2O
where "a" has a value of about 0.01 to about 5, "b" has a value of
about 0.01 to about 5, "c" has a value of about 0 to about 2, "d"
has a value of about 0.5 to about 8, "e" has a value of about 0 to
about 4, and "f" has a value from 30 to 1000. If alkoxides are
used, it is preferred to include a distillation or evaporative step
to remove the alcohol hydrolysis products.
The reaction mixture is reacted at a temperature of about
60.degree. C. to about 200.degree. C. and preferably from about
125.degree. C. to about 175.degree. C. for a period of about 1 day
to about 21 days and preferably for a time of about 2 days to about
10 days in a sealed reaction vessel at autogenous pressure. The
reaction vessel may be heated with stirring, heated while tumbling,
or heated quiescently. After crystallization is complete, the solid
product is isolated from the heterogeneous mixture by means such as
filtration or centrifugation, and then washed with deionized water
and dried in air at ambient temperature up to about 100.degree. C.
AlPO-90 seeds can optionally be added to the reaction mixture in
order to accelerate the formation of the desired microporous
composition.
The AlPO-90 aluminophosphate-based material, which is obtained from
the above-described process, is characterized by the x-ray
following diffraction pattern, having at least the d-spacings and
relative intensities set forth in Table 1:
TABLE-US-00003 TABLE 1 2-theta (.degree.) d (.ANG.) Intensity
9.86-9.91 8.96-8.91 w-m 13.97-14.10 6.34-6.28 m 17.21-17.26
5.15-5.13 vw-w 18.79-18.91 4.72-4.68 vw-w 19.78-19.87 4.49-4.46 m-s
22.19-22.33 4.01-3.97 w-m 23.57-23.63 3.78-3.76 w 24.36-24.50
3.66-3.63 vs 27.55-27.61 3.24-3.22 w-m 28.16-28.37 3.17-3.14 m
31.51-31.69 2.84-2.82 w-m 33.26-33.37 2.70-2.68 vw 34.32-34.86
2.62-2.57 w-m 42.59-42.91 2.13-2.10 vw-w 47.70-47.90 1.91-1.89 vw-w
51.92-52.37 1.76-1.74 w-m
The AlPO-90 material may be calcined in either air or nitrogen to
remove the occluded template. In one embodiment of the invention,
the AlPO-90 is calcined at a temperature of at least 550.degree. C.
In another embodiment of the invention, the AlPO-90 is calcined at
a temperature of at least 600.degree. C. In another embodiment of
the invention, the AlPO-90 is calcined at a temperature of at least
650.degree. C. The AlPO-90 is thermally stable upon calcination,
and may be characterized by the x-ray diffraction pattern, having
at least the d-spacings and relative intensities set forth in Table
2 below:
TABLE-US-00004 TABLE 2 2-theta (.degree.) d (.ANG.) Intensity
9.96-10.05 8.87-8.79 w 14.13-14.17 6.27-6.24 vs 19.23-19.32
4.62-4.59 vw-m 20.06-20.10 4.43-4.41 w-m 22.41-22.49 3.97-3.95 vw-m
24.02-24.65 3.71-3.60 m-vs 27.88-27.98 3.20-3.18 w-m 28.38-28.54
3.15-3.12 m 31.89-31.98 2.81-2.79 w 35.05-35.12 2.56-2.55 w
52.60-52.81 1.74-1.73 vw
The stable calcined AlPO-90 material can be characterized on an
anhydrous basis by the empirical formula:
H.sub.wM.sub.m.sup.2+EP.sub.xSi.sub.yO.sub.z where M is at least
one metal cation of valence +2 selected from the group consisting
of Be.sup.2+, Mg.sup.2+, Zn.sup.2+, Co.sup.2+, Mn.sup.2+,
Fe.sup.2+, Ni.sup.2+, "m" is the mole ratio of M to E and varies
from 0 to about 1.0, H is a proton, w" is the mole ratio of H to E
and varies from 0 to 2.5, E is a trivalent element selected from
the group consisting of aluminum, gallium, iron, boron and mixtures
thereof, "x" is mole ratio of P to E and varies from 0.5 to about
2.0, "y" is the mole ratio of Si to E and varies from 0 to about
1.0, and "z" is the mole ratio of 0 to E and has a value determined
by the equation: z=(2m+c+a+3+5x+4y)/2
The crystalline AlPO-90 materials of this invention can be used for
separating mixtures of molecular species, removing contaminants
through ion exchange and catalyzing various hydrocarbon conversion
processes. Separation of molecular species can be based either on
the molecular size (kinetic diameter) or on the degree of polarity
of the molecular species.
The AlPO-90 compositions of this invention can also be used as a
catalyst or catalyst support in various hydrocarbon conversion
processes. Hydrocarbon conversion processes are well known in the
art and include cracking, hydrocracking, alkylation of both
aromatics and isoparaffin, isomerization, polymerization,
reforming, hydrogenation, dehydrogenation, transalkylation,
dealkylation, hydration, dehydration, hydrotreating,
hydrodenitrogenation, hydrodesulfurization, methanol to olefins,
methanation and syngas shift process. Specific reaction conditions
and the types of feeds which can be used in these processes are set
forth in U.S. Pat. Nos. 4,310,440, 4,440,871 and 5,126,308, which
are incorporated by reference.
The AlPO-90 materials may also be used as a catalyst for the
conversion of methanol to olefins. The methanol can be in the
liquid or vapor phase with the vapor phase being preferred.
Contacting the methanol with the AlPO-90 catalyst can be done in a
continuous mode or a batch mode with a continuous mode being
preferred. The amount of time that the methanol is in contact with
the AlPO-90 catalyst must be sufficient to convert the methanol to
the desired light olefin products. When the process is carried out
in a batch process, the contact time varies from about 0.001 hrs to
about 1 hr and preferably from about 0.01 hr to about 1.0 hr. The
longer contact times are used at lower temperatures while shorter
times are used at higher temperatures. When the process is carried
out in a continuous mode, the Weight Hourly Space Velocity (WHSV)
based on methanol can vary from about 1 hr-1 to about 1000 hr-1 and
preferably from about 1 hr-1 to about 100 hr-1.
Generally, the process must be carried out at elevated temperatures
in order to form light olefins at a fast enough rate. Thus, the
process should be carried out at a temperature of about 300.degree.
C. to about 600.degree. C., preferably from about 400.degree. C. to
about 550.degree. C. and most preferably from about 435.degree. C.
to about 525.degree. C. The process may be carried out over a wide
range of pressure including autogenous pressure. Thus, the pressure
can vary from about 0 kPa (0 psig) to about 1724 kPa (250 psig) and
preferably from about 34 kPa (5 psig) to about 345 kPa (50
psig).
Optionally, the methanol feedstock may be diluted with an inert
diluent in order to more efficiently convert the methanol to
olefins. Examples of the diluents which may be used are helium,
argon, nitrogen, carbon monoxide, carbon dioxide, hydrogen, steam,
paraffinic hydrocarbons, e.g., methane, aromatic hydrocarbons,
e.g., benzene, toluene and mixtures thereof. The amount of diluent
used can vary considerably and is usually from about 5 to about 90
mole percent of the feedstock and preferably from about 25 to about
75 mole percent.
The actual configuration of the reaction zone may be any well known
catalyst reaction apparatus known in the art. Thus, a single
reaction zone or a number of zones arranged in series or parallel
may be used. In such reaction zones the methanol feedstock is
flowed through a bed containing the AlPO-90 catalyst. When multiple
reaction zones are used, one or more AlPO-90 catalysts may be used
in series to produce the desired product mixture. Instead of a
fixed bed, a dynamic bed system, (e.g., fluidized bed or moving
bed), may be used. Such a dynamic system would facilitate any
regeneration of the AlPO-90 catalyst that may be required. If
regeneration is required, the AlPO-90 catalyst can be continuously
introduced as a moving bed to a regeneration zone where it can be
regenerated by means such as oxidation in an oxygen containing
atmosphere to remove carbonaceous materials.
The AlPO-90 materials of this invention can also be used as an
adsorbent for water vapor. The adsorbent may be a component of an
adsorption heat pump apparatus. Adsorbents used for adsorption heat
pump purposes are desired to have a high capacity for water vapor,
as well as a large crystallographic density. The crystallographic
density of microporous crystalline materials is conveniently
expressed in units of T-atom/1000 .ANG..sup.3. Generally speaking,
adsorbents with a low density can be problematic since they would
require a large volume of material to take up a given quantity of
adsorbate. This can be troublesome if space is limited in the
application. It is thus of interest to consider uptake capacity on
a volumetric basis as opposed to a gravimetric basis.
The following examples are presented in illustration of this
invention and are not intended as undue limitations on the
generally broad scope of the invention as set out in the appended
claims. The products will be designated with names that contain the
suffix "-90" to indicate the "-90" structure and prefix that
reflects the compositional nature of the product, such as "SAPO"
for a silicoaluminophosphate, "ZnAPO" for a zinc aluminophosphate,
and "MgAPSO" for a magnesium silicoaluminophosphate, etc.
The structure of the AlPO-90 compositions of this invention was
determined by x-ray analysis. The x-ray patterns presented in the
following examples were obtained using standard x-ray powder
diffraction techniques. The radiation source was a high-intensity,
x-ray tube operated at 45 kV and 35 mA. The diffraction pattern
from the copper K-alpha radiation was obtained by appropriate
computer based techniques. Flat compressed powder samples were
continuously scanned at 2.degree. to 56.degree. (2.theta.).
Interplanar spacings (d) in Angstrom units were obtained from the
position of the diffraction peaks expressed as .theta. where
.theta. is the Bragg angle as observed from digitized data.
Intensities were determined from the integrated area of diffraction
peaks after subtracting background, "I.sub.o" being the intensity
of the strongest line or peak, and "I" being the intensity of each
of the other peaks.
As will be understood by those skilled in the art, the
determination of the parameter 2.theta. is subject to both human
and mechanical error, which in combination can impose an
uncertainty of about .+-.0.4.degree. on each reported value of
2.theta.. This uncertainty is, of course, also manifested in the
reported values of the d-spacings, which are calculated from the
2.theta. values. This imprecision is general throughout the art and
is not sufficient to preclude the differentiation of the present
crystalline materials from each other and from the compositions of
the prior art. In some of the x-ray patterns reported, the relative
intensities of the d-spacings are indicated by the notations vs, s,
m, w, and vw which represent very strong, strong, medium, weak, and
very weak respectively. In terms of 100.times.I/I.sub.o, the above
designations are defined as: vw=0-5; w=5-15; m=15-40: s=40-75 and
vs=75-100
In certain instances the purity of a synthesized product may be
assessed with reference to its x-ray powder diffraction pattern.
Thus, for example, if a sample is stated to be pure, it is intended
only that the x-ray pattern of the sample is free of lines
attributable to crystalline impurities, not that there are no
amorphous materials present.
In order to more fully illustrate the invention, the following
examples are set forth. It is to be understood that the examples
are only by way of illustration and are not intended as an undue
limitation on the broad scope of the invention as set forth in the
appended claims.
EXAMPLE 1
468.1 g of water was added to a three-necked 2-liter round bottom
flask equipped with a condenser, overhead mixer, thermocouple, and
a nitrogen blanket over the top of the condenser. The flask was
placed in an ice bath. 261.7 g of 1,4-dibromobutane (99%) was added
to the flask. The temperature of the mixture reached 8.degree. C.
before 206.4 g of piperidine (99%) was slowly added. The
temperature of the mixture was 29.degree. C. after addition of the
piperidine, then steadily rose to a peak temperature of 70.degree.
C. Once the temperature started dropping from its peak, the cloudy
white mixture became clear, and was mixed for an additional 2
hours.
EXAMPLE 2
885 g of the product from Example 1 was added to a three-necked 2
liter round bottom flask equipped with an overhead mixer. 283.9 g
of Ag.sub.2O was added to the flask and stirred at room temperature
for 1 day. The mixture is grey in color. The mixture was then
filtered to remove precipitated silver bromide. The remaining
mixture was then analyzed for water content, which showed it was
70.5% water.
EXAMPLE 3
20.11 g of the product from Example 1 was combined with 2.37 g of
tetramethylammonium hydroxide (TMAOH; Sigma-Aldrich, 25%). 1.94 g
of Al(OH).sub.3 (Pfaltz & Bauer) was then added to the mixture
followed by 0.22 g of Ludox AS-40 (Sigma-Aldrich, 40% SiO.sub.2).
5.36 g of phosphoric acid (Fisher; 85%) was then slowly added. The
material was then mixed for 30 minutes. The mixture was then
transferred to a 45 cc autoclave and held at 170.degree. C. in a
tumble oven for 3 days. After cooling to room temperature, the
material was isolated via centrifugation and dried at 100.degree.
C. overnight. ICP analysis showed a composition of 1.70% Si, 21.2%
Al, 24.6% P (weight percent). CHN analysis showed 12.6% C, 2.89% H,
2.45% N (weight percent). XRD analysis of the material gave the
following peaks:
TABLE-US-00005 2-Theta d (.ANG.) Intensity 9.8883 8.9377 w 13.9716
6.3334 m 17.2166 5.1463 vw 18.7904 4.7187 w 19.7852 4.4836 s
22.1931 4.0023 w 23.5708 3.7714 w 24.3648 3.6503 vs 27.5523 3.2348
w 28.1685 3.1654 m 31.5141 2.8366 m 33.2654 2.6911 vw 34.6595 2.586
w 40.246 2.239 vw 42.9014 2.1064 w 47.7024 1.905 w 51.9222 1.7596
m
This material was determined to be SAPO-90 by XRD.
EXAMPLE 4
20.26 g of the product from Example 1 was combined with 2.39 g of
tetramethylammonium hydroxide (TMAOH; Sigma-Aldrich, 25%). 1.96 g
of Al(OH).sub.3 (Pfaltz & Bauer) was then added to the mixture
followed by 5.4 g of phosphoric acid (Fisher; 85%) slowly. The
material was mixed for 30 minutes. The mixture was then transferred
to a 45 cc autoclave and held at 160.degree. C. in a tumble oven
for 2 days. After cooling to room temperature, the material was
isolated via centrifugation and dried at 100.degree. C. overnight.
XRD analysis of the material gave the following peaks:
TABLE-US-00006 2-Theta d (.ANG.) Intensity 9.9092 8.9189 m 14.0904
6.2803 m 17.2562 5.1346 w 18.9086 4.6895 vw 19.8646 4.4659 m
22.3234 3.9792 m 23.6282 3.7624 w 24.4941 3.6313 vs 27.6099 3.2282
m 28.3668 3.1437 m 31.6819 2.8219 w 33.3349 2.6857 vw 34.3206
2.6108 w 34.8282 2.5739 w 42.6232 2.1195 vw 43.1211 2.0961 w
47.8905 1.8979 vw 52.3698 1.7456 w
The product was determined to be AlPO-90 by XRD.
EXAMPLE 5
20.26 g of the product from Example 1 was combined with 2.39 g of
tetramethylammonium hydroxide (TMAOH; Sigma-Aldrich, 25%). 1.96 g
of Al(OH).sub.3 (Pfaltz & Bauer) was then added to the mixture
followed by 5.4 g of phosphoric acid (Fisher; 85%) slowly. The
material was mixed for 30 minutes. The mixture was then transferred
to a 45 cc autoclave and held at 170.degree. C. in a tumble oven
for 2 days. After cooling to room temperature, the material was
isolated via centrifugation and dried at 100.degree. C. overnight.
XRD analysis of the material gave the following peaks:
TABLE-US-00007 2-Theta d (.ANG.) Intensity 9.8694 8.9548 m 14.0805
6.2847 m 17.2366 5.1404 w 18.8794 4.6966 w 19.8548 4.4681 m 22.2939
3.9844 m 23.6083 3.7655 w 24.4742 3.6342 vs 27.6004 3.2293 m
28.3469 3.1459 m 31.6522 2.8245 w 33.3643 2.6834 vw 34.3506 2.6086
w 34.8576 2.5718 w 42.5946 2.1208 vw 43.0913 2.0975 w 47.82 1.9005
vw 52.3299 1.7469 w
The product was determined to be AlPO-90 by XRD.
EXAMPLE 6
13.34 g of water was combined with 93.89 g of the product from
Example 1 followed by 12.66 g of tetramethylammonium hydroxide
(TMAOH; Sigma-Aldrich, 25%). 10.37 g of Al(OH).sub.3 (Pfaltz &
Bauer) was then added to the mixture followed by 1.17 g of Ludox
AS-40 (Sigma-Aldrich, 40% SiO.sub.2) and 28.60 g of phosphoric acid
(Fisher; 85%) slowly. The material was mixed for 30 minutes. The
mixture was then transferred to a 300 cc stirred autoclave and held
at 170.degree. C. for 2 days with a stir rate of 300 rpm. After
cooling to room temperature, the material was isolated via
centrifugation and dried at 100.degree. C. overnight. ICP analysis
showed a composition of 1.66% Si, 20.7% Al, 25.4% P (weight
percent). XRD analysis of the material gave the following
peaks:
TABLE-US-00008 2-Theta d (.ANG.) Intensity 9.8692 8.955 w 14.0209
6.3113 m 17.2355 5.1407 vw 19.8051 4.4792 m 22.1942 4.0021 w
24.3648 3.6503 vs 27.561 3.2338 w 28.2375 3.1578 m 31.6023 2.8289 w
33.2637 2.6913 vw 34.6887 2.5839 m 40.2936 2.2365 vw 42.7826 2.1119
w 47.7112 1.9046 vw 52.0912 1.7543 w
The product was determined to be SAPO-90 by XRD.
EXAMPLE 7
The product from Example 3 was calcined in air at 600.degree. C.
for 4 hours in a muffle furnace. The temperature was ramped up to
600.degree. C. at a rate of 2.degree. C./min. The material was then
cooled to room temperature. XRD analysis of the material gave the
following peaks:
TABLE-US-00009 2-Theta d (.ANG.) Intensity 10.0499 8.7944 w 14.1305
6.2626 vs 19.2316 4.6114 vw 20.0628 4.4222 w 22.4897 3.9502 vw
24.5834 3.6183 s 27.8886 3.1965 w 28.3884 3.1414 m 31.8925 2.8038 w
35.0573 2.5576 w 52.6388 1.7373 vw
The calcined SAPO-90 product was pressed into a pellet and loaded
in a McBain gravimetric balance for adsorption studies. It was
observed that the SAPO-90 took up 14.3% water by weight and 3.0%
n-butane by weight.
EXAMPLE 8
The product from Example 4 was calcined in air at 650.degree. C.
for 8 hours in a muffle furnace. The temperature was ramped up to
650.degree. C. at a rate of 1-2.degree. C./min. The material was
then cooled to room temperature. XRD analysis of the material gave
the following peaks:
TABLE-US-00010 2-Theta d (.ANG.) Intensity 10.0089 8.8303 w 14.1602
6.2495 vs 17.2659 5.1317 vw 19.3174 4.5911 m 20.0739 4.4198 m
22.4733 3.953 m 24.0265 3.7009 m 24.6434 3.6096 vs 27.9788 3.1864 m
28.5356 3.1255 m 31.9707 2.7971 w 33.6032 2.6648 vw 35.1167 2.5534
w 52.8083 1.7322 vw
EXAMPLE 9
The product from Example 5 was calcined in air at 650.degree. C.
for 8 hours in a muffle furnace. The temperature was ramped up to
650.degree. C. at a rate of 1-2.degree. C./min. The material was
then cooled to room temperature. XRD analysis of the material gave
the following peaks:
TABLE-US-00011 2-Theta d (.ANG.) Intensity 9.9987 8.8393 w 14.1601
6.2495 vs 17.3757 5.0996 vw 19.3271 4.5888 m 20.0938 4.4155 m
22.4628 3.9548 w 24.0262 3.7009 m 24.6534 3.6082 s 27.9588 3.1887 m
28.5061 3.1287 m 31.9908 2.7954 w 33.5239 2.671 vw 35.1566 2.5506 w
52.8279 1.7316 vw
EXAMPLE 10
The product from Example 6 was calcined in air at 650.degree. C.
for 8 hours in a muffle furnace. The temperature was ramped up to
650.degree. C. at a rate of 1-2.degree. C./min. The material was
then cooled to room temperature. XRD analysis of the material gave
the following peaks:
TABLE-US-00012 2-Theta d (.ANG.) Intensity 9.9696 8.865 w 14.1502
6.2539 vs 20.0939 4.4154 w 22.4128 3.9636 vw 24.6037 3.6154 s
27.9481 3.1899 w 28.4562 3.134 m 31.9111 2.8022 w 35.0572 2.5576 w
52.6095 1.7382 vw
COMPARATIVE EXAMPLE 1
9.49 g of water was combined with 12.58 g of tetramethylammonium
hydroxide (TMAOH; Sigma-Aldrich, 25%). 2.07 g of Al(OH).sub.3
(Pfaltz & Bauer) was then added to the mixture followed 0.25 g
of Ludox AS-40 (Sigma-Aldrich, 40% SiO.sub.2). 5.70 g of phosphoric
acid (Fisher; 85%) was then slowly added. The material was mixed
for 30 minutes. The mixture was then transferred to a 45 cc
autoclave and held at 170.degree. C. in a tumble oven for 3 days.
After cooling to room temperature, the material was isolated via
centrifugation and dried at 100.degree. C. overnight. XRD analysis
of the material showed that it was AlPO-20 (SOD structure).
SPECIFIC EMBODIMENTS
While the following is described in conjunction with specific
embodiments, it will be understood that this description is
intended to illustrate and not limit the scope of the preceding
description and the appended claims.
A first embodiment of the invention is a microporous crystalline
material that has an empirical composition in an as-synthesized
form and on an anhydrous basis expressed by an empirical formula
C.sup.+.sub.cA.sup.+.sub.aM.sub.m.sup.2+EP.sub.xSi.sub.yO.sub.z
where M is at least one framework divalent cation and is selected
from the group consisting of alkaline earth and transition metals,
wherein M is a cation selected from the group consisting of
beryllium, magnesium, cobalt (II), manganese, zinc, iron(II),
nickel and mixtures thereof, C is a cyclic organoammonium cation, A
is an acyclic organoammonium cation, the ratio (c/a) having a value
from 0.01 to about 100, and the sum (c+a) representing the mole
ratio of (C+A) to E and has a value of about 0.1 to about 2.0, "m"
is the mole ratio of M to E and varies from 0 to about 1.0, "x" is
a mole ratio of P to E and varies from 0.5 to about 2.0, a ratio of
silicon to E is represented by "y" which varies from about 0 to
about 1.0, E is a trivalent element which is tetrahedrally
coordinated, is present in the framework, and is selected from the
group consisting of aluminum, gallium, iron(III) and boron and "z"
is a mole ratio of 0 to E and is given by an equation
z=(2m+c+a+3+5x+4y)/2 and is characterized by a following x-ray
diffraction pattern, having at least the d-spacings and relative
intensities set forth in Table 1.
TABLE-US-00013 TABLE 1 2-theta (.degree.) d (.ANG.) Intensity
9.86-9.91 8.96-8.91 w-m 13.97-14.10 6.34-6.28 m 17.21-17.26
5.15-5.13 vw-w 18.79-18.91 4.72-4.68 vw-w 19.78-19.87 4.49-4.46 m-s
22.19-22.33 4.01-3.97 w-m 23.57-23.63 3.78-3.76 w 24.36-24.50
3.66-3.63 vs 27.55-27.61 3.24-3.22 w-m 28.16-28.37 3.17-3.14 m
31.51-31.69 2.84-2.82 w-m 33.26-33.37 2.70-2.68 vw 34.32-34.86
2.62-2.57 w-m 42.59-42.91 2.13-2.10 vw-w 47.70-47.90 1.91-1.89 vw-w
51.92-52.37 1.76-1.74 w-m
An embodiment of the invention is one, any or all of prior
embodiments in this paragraph up through the first embodiment in
this paragraph wherein after being calcined the AlPO-90 material is
characterized by the x-ray diffraction pattern, having at least the
d-spacings and relative intensities set forth in Table 2 below.
TABLE-US-00014 TABLE 2 2-theta (.degree.) d (.ANG.) Intensity
9.96-10.05 8.87-8.79 w 14.13-14.17 6.27-6.24 vs 19.23-19.32
4.62-4.59 vw-m 20.06-20.10 4.43-4.41 w-m 22.41-22.49 3.97-3.95 vw-m
24.02-24.65 3.71-3.60 m-vs 27.88-27.98 3.20-3.18 w-m 28.38-28.54
3.15-3.12 m 31.89-31.98 2.81-2.79 w 35.05-35.12 2.56-2.55 w
52.60-52.81 1.74-1.73 vw
An embodiment of the invention is one, any or all of prior
embodiments in this paragraph up through the first embodiment in
this paragraph wherein the AlPO-90 material is characterized on an
anhydrous basis by the empirical formula
H.sub.wM.sub.m.sup.2+EP.sub.xSi.sub.yO.sub.z where M is at least
one metal cation of valence +2 selected from the group consisting
of Be.sup.2+, Mg.sup.2+, Zn.sup.2+, Co.sup.2+, Mn.sup.2+,
Fe.sup.2+, Ni.sup.2+, "m" is the mole ratio of M to E and varies
from 0 to about 1.0, H is a proton, w" is the mole ratio of H to E
and varies from 0 to 2.5, E is a trivalent element selected from
the group consisting of aluminum, gallium, iron, boron and mixtures
thereof, "x" is mole ratio of P to E and varies from 0.5 to about
2.0, "y" is the mole ratio of Si to E and varies from 0.05 to about
1.0, "m"+"y">0.1, and "z" is the mole ratio of 0 to E and has a
value determined by the equation z=(w+2m+3+5x+4y)/2. An embodiment
of the invention is one, any or all of prior embodiments in this
paragraph up through the first embodiment in this paragraph wherein
the microporous crystalline material indexes on a unit cell with
hexagonal axes with lattice parameters a=12.768 .ANG. and c=15.333
.ANG. and has an ABC-6 net structure with the stacking sequence
repeating every 6 layers along the c-axis (p=15.333/2.5=6.13). An
embodiment of the invention is one, any or all of prior embodiments
in this paragraph up through the first embodiment in this paragraph
wherein the microporous crystalline material can be described as a
combination of two zeotypes with stacking sequences of AABCBC and
ABACBC. An embodiment of the invention is one, any or all of prior
embodiments in this paragraph up through the first embodiment in
this paragraph wherein the microporous crystalline material has a
percentage of AABCBC zeotype that can be defined as x and the
percentage of ABACBC zeotype can be defined as (100-x), where x
ranges from 0-100, inclusive.
A second embodiment of the invention is a method of making a
AlPO-90 microporous crystalline material comprising preparing a
reaction mixture containing reactive sources described in terms of
molar ratios of the oxides by a formula aA.sub.2O bC.sub.2O cMO
E.sub.2O.sub.3 dP.sub.2O.sub.5 eSiO.sub.2 fH.sub.2O where "a" has a
value of about 0.01 to about 5, "b" has a value of about 0.01 to
about 5, "c" has a value of about 0 to about 2, "d" has a value of
about 0.5 to about 8, "e" has a value of about 0 to about 4, and
"f" has a value from 30 to 1000, wherein reactive sources of C, A,
E, phosphorus and one or both M and silicon; reacting the reaction
mixture at a temperature from about 60.degree. C. to about
200.degree. C. for a period of about 1 day to about 21 days; and
isolating a solid product from a heterogeneous mixture wherein the
AlPO-90 microporous material, is characterized by the x-ray
following diffraction pattern, having at least the d-spacings and
relative intensities set forth in Table 1:
TABLE-US-00015 TABLE 1 2-theta (.degree.) d (.ANG.) Intensity
9.86-9.91 8.96-8.91 w-m 13.97-14.10 6.34-6.28 m 17.21-17.26
5.15-5.13 vw-w 18.79-18.91 4.72-4.68 vw-w 19.78-19.87 4.49-4.46 m-s
22.19-22.33 4.01-3.97 w-m 23.57-23.63 3.78-3.76 w 24.36-24.50
3.66-3.63 vs 27.55-27.61 3.24-3.22 w-m 28.16-28.37 3.17-3.14 m
31.51-31.69 2.84-2.82 w-m 33.26-33.37 2.70-2.68 vw 34.32-34.86
2.62-2.57 w-m 42.59-42.91 2.13-2.10 vw-w 47.70-47.90 1.91-1.89 vw-w
51.92-52.37 1.76-1.74 w-m
An embodiment of the invention is one, any or all of prior
embodiments in this paragraph up through the first embodiment in
this paragraph wherein the AlPO-90 is calcined at a temperature of
at least 550.degree. C. and is characterized by the x-ray
diffraction pattern, having at least the d-spacings and relative
intensities set forth in Table 2 below:
TABLE-US-00016 TABLE 2 2-theta (.degree.) d (.ANG.) Intensity
9.96-10.05 8.87-8.79 w 14.13-14.17 6.27-6.24 vs 19.23-19.32
4.62-4.59 vw-m 20.06-20.10 4.43-4.41 w-m 22.41-22.49 3.97-3.95 vw-m
24.02-24.65 3.71-3.60 m-vs 27.88-27.98 3.20-3.18 w-m 28.38-28.54
3.15-3.12 m 31.89-31.98 2.81-2.79 w 35.05-35.12 2.56-2.55 w
52.60-52.81 1.74-1.73 vw
An embodiment of the invention is one, any or all of prior
embodiments in this paragraph up through the first embodiment in
this paragraph wherein the sources of aluminum are selected from
the group consisting of aluminum alkoxides, precipitated aluminas,
aluminum metal, aluminum hydroxide, aluminum salts and alumina
sols. An embodiment of the invention is one, any or all of prior
embodiments in this paragraph up through the first embodiment in
this paragraph wherein sources of phosphorus are selected from the
group consisting of orthophosphoric acid, phosphorus pentoxide, and
ammonium dihydrogen phosphate. An embodiment of the invention is
one, any or all of prior embodiments in this paragraph up through
the first embodiment in this paragraph wherein sources of silica
are selected from the group consisting of tetraethylorthosilicate,
colloidal silica, and precipitated silica. An embodiment of the
invention is one, any or all of prior embodiments in this paragraph
up through the first embodiment in this paragraph wherein sources
of E elements are selected from the group consisting of
organoammonium borates, boric acid, precipitated gallium
oxyhydroxide, gallium sulfate, ferric sulfate, and ferric chloride.
An embodiment of the invention is one, any or all of prior
embodiments in this paragraph up through the first embodiment in
this paragraph wherein sources of the M metals are selected from
the group consisting of halide salts, nitrate salts, acetate salts,
and sulfate salts of the respective alkaline earth and transition
metals. An embodiment of the invention is one, any or all of prior
embodiments in this paragraph up through the first embodiment in
this paragraph wherein C is an organoammonium cation prepared from
a reaction of an aqueous mixture of a cyclic secondary amine and an
organic dihalide. An embodiment of the invention is one, any or all
of prior embodiments in this paragraph up through the first
embodiment in this paragraph wherein the cyclic secondary amines
are selected from the group consisting of piperidine,
homopiperidine, pyrrolidine, and morpholine. An embodiment of the
invention is one, any or all of prior embodiments in this paragraph
up through the first embodiment in this paragraph wherein A is an
acyclic organoammonium cation represented as NR.sub.4.sup.+. An
embodiment of the invention is one, any or all of prior embodiments
in this paragraph up through the first embodiment in this paragraph
wherein the R groups are, independently, aliphatic carbon chains of
the formula C.sub.nH.sub.2n+1, where n is a whole number ranging
from 1 to 4, inclusive. An embodiment of the invention is one, any
or all of prior embodiments in this paragraph up through the first
embodiment in this paragraph wherein the AlPO-90 microporous
crystalline material is calcined at a temperature of at least
600.degree. C. An embodiment of the invention is one, any or all of
prior embodiments in this paragraph up through the first embodiment
in this paragraph wherein the AlPO-90 microporous crystalline
material is calcined at a temperature of at least 650.degree.
C.
A third embodiment of the invention is a process of separating
mixtures of molecular species, removing contaminants or catalyzing
hydrocarbon conversion processes comprising contacting a feed
stream with a microporous crystalline material that has an
empirical composition in a calcined form and on an anhydrous basis
expressed by an empirical formula
H.sub.wM.sub.m.sup.2+EP.sub.xSi.sub.yO.sub.z where M is at least
one framework divalent cation and is selected from the group
consisting of alkaline earth and transition metals, wherein M is a
cation selected from the group consisting of beryllium, magnesium,
cobalt (II), manganese, zinc, iron(II), nickel and mixtures
thereof. H is a proton, w" is the mole ratio of H to E and varies
from 0 to 2.5, "m" is the mole ratio of M to E and varies from 0 to
about 1.0, "x" is a mole ratio of P to E and varies from 0.5 to
about 2.0, a ratio of silicon to E is represented by "y" which
varies from about 0 to about 1.0, E is a trivalent element which is
tetrahedrally coordinated, is present in the framework, and is
selected from the group consisting of aluminum, gallium, iron(III)
and boron and "z" is a mole ratio of O to E and is given by an
equation z=(2m+r+3+5x+4y)/2 and is characterized by an x-ray
following diffraction pattern, having at least the d-spacings and
relative intensities set forth in Table 2
TABLE-US-00017 TABLE 2 2-theta (.degree.) d (.ANG.) Intensity
9.96-10.05 8.87-8.79 w 14.13-14.17 6.27-6.24 vs 19.23-19.32
4.62-4.59 vw-m 20.06-20.10 4.43-4.41 w-m 22.41-22.49 3.97-3.95 vw-m
24.02-24.65 3.71-3.60 m-vs 27.88-27.98 3.20-3.18 w-m 28.38-28.54
3.15-3.12 m 31.89-31.98 2.81-2.79 w 35.05-35.12 2.56-2.55 w
52.60-52.81 1.74-1.73 vw
An embodiment of the invention is one, any or all of prior
embodiments in this paragraph up through the second embodiment in
this paragraph wherein the separation of molecular species is in an
operation of an adsorption heat pump wherein water vapor is
adsorbed by the microporous crystalline material. An embodiment of
the invention is one, any or all of prior embodiments in this
paragraph up through the second embodiment in this paragraph
wherein the hydrocarbon conversion processes are selected from the
group consisting of cracking, hydrocracking, alkylation of both
aromatics and isoparaffin, isomerization, polymerization,
reforming, hydrogenation, dehydrogenation, transalkylation,
dealkylation, hydration, dehydration, hydrotreating,
hydrodenitrogenation, hydrodesulfurization, methanol to olefins,
methanation and a syngas shift process. An embodiment of the
invention is one, any or all of prior embodiments in this paragraph
up through the second embodiment in this paragraph wherein the
separation of molecular species is based on the molecular size
(kinetic diameter) or on the degree of polarity of the molecular
species.
* * * * *